Homogeneity and Canonical Connections of Isoparametric Manifolds

On every isoparametric submanifold M a connection with parallel second fundamental form is constructed geometrically such that M is an orbit of an s-representation if and only if the connection is a canonical one. If the rank of M is greater than one this connection is in case of homogeneity the canonical connection of the reductive decomposition given by the orbit of s-representation. This revised version was published online in June 2006 with corrections to the Cover Date.     

Non-destructive determination of plutonium in nuclear fuel rods and pellets

Analytical and Bioanalytical Chemistry - A non-destructive method and an experimental set-up are described by which the Pu content in UO2/PuO2 mixed oxide (MOX) pellets and in fuel rods,...     

MgF(3)(-) as a transition state analog of phosphoryl transfer

The formation of complexes between small G proteins and certain of their effectors can be facilitated by aluminum fluorides. Solution studies suggest that magnesium may be able to replace aluminum in such complexes. We have determined the crystal structure of RhoA.GDP bound to RhoGAP in the presence of Mg(2+) and F(-) but without Al(3+). The metallofluoride adopts a trigonal planar arrangement instead of the square planar structure of AlF(4)(-). We have confirmed that these crystals contain magnesium and not aluminum by proton-induced X-ray emission spectroscopy. The structure adopted by GDP.MgF(-) possesses the stereochemistry and approximate charge expected for the transition state. We suggest that MgF3(-) may be the reagent of choice for studying phosphoryl transfer reactions.     

Laccase-catalyzed carbon-carbon bond formation: oxidative dimerization of salicylic esters by air in aqueous solution

The laccase catalyzed oxidative dimerization of salicylic esters, a rare example of a laccase-catalyzed carbon-carbon bond formation, was studied. This reaction allows the use of air as stoichiometric oxidant and proceeds in aqueous solution. The preparative scope and the mechanism of the method, which provides a new and convenient access to functionalized biaryls under mild conditions, were investigated.     

Definitive Proof for the Operation of Isotopically Sensitive Branching (‘Metabolic Switching’) in FeI-Mediated C?H Bond Activation in the Gas Phase Short Communication

Rigorous regio- and stereospecific labeling experiments are performed to demonstrate the operation of the previously suggested operation of ‘isotopically sensitive branching’ in Fe^I-mediated C? H bond activation. For the hexane-1,6-diol/Fe⁺-complex, it is shown that dehydrogenation involves specifically the central C(3)/C(4) position, and the study of the stereospecifically labeled D ,L - and meso-[3,4-D₂]-isotompomers 1e and 1f demonstrates that dehydrogenation proceedes via two competing pathways (i.e. ‘anti’- vs. ‘syn’-route). The contribution of these routes to the product formation is – due to a kinetic isotope effect – controlled by the relative configuration at the labeled positions C(3)/C(4). For the D ,L -form 1e , we estimate a ratio of 49:1 in favor of the ‘anti’-route; due to an isotope effect, this ratio drops to 4.3:1 for the meso-form 1f .     

Small-angle X-ray scattering studies of the open and closed conformations of aspartate aminotransferase

Summary Aspartate aminotransferase was investigated by X-ray small-angle scattering. A small difference was found between the open (active) and the closed (liganded) conformation of the enzyme. The results were compared with X-ray crystallography data.

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Untersuchungen zur Röntgenkleinwinkelstreuung der offenen und geschlossenen Konformation von Aspartat-Aminotransferase

Zusammenfassung Aspartat-Aminotransferase wurde mittels Röntgenkleinwinkelstreuung untersucht. Ein kleiner Unterschied zwischen der offenen (aktiven) und der geschlossenen (ligandierten) Konformation wurde gefunden. Die Ergebnisse wurden mit Röntgenkristallstrukturdaten verglichen.

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Abbreviations AspAT aspartate aminotransferase     

Buchbesprechungen

Ohne Zusammenfassung     

A new inorganic-organic polymer for the passivation of thin film capacitors

Inorganic-organic polymers with barrier properties against water vapor, excellent electrical data (3, 2, R _D>10¹⁶ cm, E _D up to 400 V/µm) and good adhesion to various substrate materials have been developed. Tailored modifications of these materials provide an excellent protective coating for thin film capacitors. Several mm thick, expensive, encapsulations could be replaced by thin coatings (up to 10 µm). The polymer coating allows the use of thin film chip capacitors in surface-mount technology. As a measure for the efficiency of the coating, the capacitance decrease under controlled humidity has been used. The influence of the material composition, the type of catalyst during sol-gel processing and the curing conditions have been studied. Adhesion and water vapor permeation properties of the polymers and rheological properties of the coating solutions have been investigated. A protective coating is developed, which increases the withstandness of capacitors against humid conditions (90°C, 100% rel. humidity) by a factor of about 30 (compared to uncoated capacitors) and shows no crack formation during thermal cycling.     

Gas Phase Catalysis by Metal Nanoparticles in Nanoporous Alumina Membranes

Nanoporous alumina membranes, loaded with palladium and ruthenium nanoparticles of various size, were used for gas phase hydrogenation of 1, 3‐butadiene and for oxidation of carbon monoxide, respectively. Those membranes contain 10⁹ ‐ 10¹¹ pores per cm², all running perpendicular to the surface. Membrane discs of 20 mm in diameter and only 60 μm thick, incorporated in a reactor in which the reactants can be pumped in a closed circuit through the pores, turned out to very actively catalyze hydrogenation of butadiene (Pd) and oxidation of CO (Ru). The activity of the Pd catalysts depends characteristically on the particles size, the gas flow, and of the educts ratio. As could be expected, larger particles are less active than smaller ones, whereas increasing gas flows in case of hydrogenation accelerates the reactions. Excessive hydrogen reduces selectivity with respect to the various butenes, but favours formation of butane.